Metal-complex dyestuffs



United States Patent This invention relates to metal-complex dyestuffsproduced either by treating with a metal-yielding agent a monoazocompound of the formula arylene-C O OH wherein R stands for a hydrogenatom or a low molecular alkyl radical,

x for an alkyl, cycloalkyl, aralkyl or aryl radical which may besubstituted with non-water-solubilizing substituents,

y for a carbonyl or sulfonyl group, 1

2, when y is a carbonyl group, for a simple linkage or, when y is -asulfonyl group, for a simple linkage or an -NH-- or N(alkyl)-- group oflow molecular weight,

arylene represents phenylene or naphthylene, and wherein the nucleus Aand the arylene radical may contain further non-water-solubilizingsubstituents, or by treating with a metal-yielding agent a mixture oftwo or more monoazo dyestuffs of the Formula I but different from eachother or a mixture of at least one monoazo compound of the above FormulaI and one or more metallizable monoazo or disazo compounds.

The metallization is carried outin such a manner that a metal-containingazo dyestufi or a mixture of metalcontaining azo dyestuifs is obtained,in which less, than two metal atoms are linked to two molecules of theazo compound in complex combination.

By metallizing a mixture of two or more different monoazo compounds ofFormula I or a mixture of at least one monoazo compound conforming tothe above definition and one or more metallizable monoazo or disazocompounds of a. different constitution, valuable mixed metalcomplexdyestuffs are obtained, the shade and dyeing properties of which can toa great extent be adjusted to the particular use in view by changing thestarting mixture of azo compounds.

The following may be enumerated as examples of suitable substituents x:alkyl radicals with one to five carbon atoms, hydroxyal-kyl,methoxyalkyl or ethoxyalkyl radicals with two to five carbon atoms,cyclohexyl, methylcyclohexyl, benzyl, phenylethyl and, in particular,phenyl, naphthyl and tetrahydronaphthyl radicals which may containchlorine atoms, methyl and methoxy radicals.

Halogen atoms preferably chlorine atoms, the methyl, methoxy or nitrogroups are of primary interest as substituents of the phenylene ornaphthylene radicals.

The metallization of the monoazo compounds of Formula l and theirmixtures in conjunction with other metalphatic monocarboxylic acid. Itis advantageous to proportion the starting materials so that an amountof metalyielding agent containing less than two but at least one atom ofmetal acts upon two molecules of azo dyestuffs.

Suitable chromium compounds are e. g. chromic fluoride, chromic sulfate,chromic formate, chromic acetate, chromic potassium sulfate and chromicammonium sulfate. The chromates, e.g. sodium chromate or bichromate,potassium chromate or bichromate, are likewise highly suitable formetallizing the monoazo dyestuffs of Formula I and their mixtures inconjunction with other metallizable monoazo or disazo compounds. In thelatter case, i.e. when chromates are used, it is advisable to work in astrongly caustic alkaline medium, to which reducing agents can be addedif necessary.

Suitable cobalt compounds are e.g. cobaltous formate, cobaltous acetateand cobaltous sulfate. When metallization is carried out in theconcentrated aqueous solution of an alkali-metal salt of a low molecularahphatic monocarboxylic acid, water-insoluble metal compounds also canbe employed, for example cobalt hydroxide or cobalt carbonate.

It is especially advantageous to carry out metallization in an aqueousor alkaline medium to which the metal compounds are added in presence ofcompounds which maintain the metal dissolved in complex combination incaustic alkaline medium, e.g. tartaric acid, citric acid and lacticacid.

The metal-complex compounds thus obtained are se arated from the aqueousmedium by the addition of salt, if necessary after previously runningthe organic metal lizing solution into water, and are subsequentlyfiltered oil, washed if necessary and dried.

The metal-containing azo dyestuffs obtained are homogeneous or mixedmetal-complex compounds in which essentially one atom of metal iscombined with two molecules of the azo compound. The metal-complexcompounds are in the main so-called 1:2 complexes wherein 1 molecule ofthe azo compound is combined with approximately 0.3 to 0.7 molecule ofmetal. The most interesting metal complex dyestufis are those which arederived from monoazo compounds of Formula I having weights between 500and 600.

The homogeneous or mixed metal-containing azo dyestuffs are soluble tomore than 20 g./l. in water and dye wool, silk, synthetic polyamidefibers and leather from neutral or weakly acid dyebaths in green, blue,violet, gray, black or brown shades which are fast to light, washing,acid and alkaline milling, perspiration, water, sea water, potting,carbonizing, decatizing, chlorine, cross dyeing, peroxide bleaching,crocking, acids, alkalis, pressing, dry cleaning and heat treatments. Ofcourse they also can be used for padding and printing these samematerials.

lizable monoazo or disazo compounds is effected prefer- Those whichpossess sufficiently high solubility in organic solvents e.g. acetone,methylene chloride and dimethylfor-mamide are also suitable for the masscoloration of artificial fibers spun from their solutions in organicsolvents and of lacquers and plastics of all kinds.

In the following examples all parts and percentages are by Weight andthe temperatures are in degrees .centigrade.

EXAMPLE 1 30.8 parts of 2-amino-l-hydroxybenzene-4-sulfonicacid-(2'-carboxy) -phenylamide are dissolved with 6 parts of sodiumhydroxide in 60 parts of water. After the addition of 6.9 parts ofsodium nitrite the solution is dropped with cooling into 40 parts of 30%hydrochloric acid and 40 parts of ice-water. The resulting suspension ofthe yellow diazo compound is heated to 50, upon which a solution of 21.9parts of 2-phenylaminonaphthalene in parts of isopropyl alcohol is addeddrop- Paten ted June 19, 1962 V powdered.

To convert the red powder into the corresponding 1:2 chromium complexcompound it is heated at 130 in 200 parts of formamide with the additionof parts of crystallized chromic potassium sulfate. After 1 hourmetallization is completed and the chromium-containing dyestutt' formedis precipitated by diluting the mass with 300 parts of concentratedsodium chloride solution. It is filtered oil and the filter cakedissolved with 16 parts of sodium hydroxide in 1000 parts of water, thechromiumcontaining azo dyestufi again precipitated by the addition ofcommon salt, filtered ofi, dried and ground. It is a dark powder whichis soluble in water (about 50 g./l.) and dyes wool, silk, syntheticpolyamide fibers and leather from neutral to weakly acid baths inneutral gray shades.

To convert the metal-free monoazo compound into the 1:2 cobalt complexcompound it is dissolved with 8 parts of sodium hydroxide in 1000 partsof water at 60 A mixture of 14.2 parts of crystallized c obaltoussulfate, 6 parts of sodium hydroxide and 126 parts of a 3% aqueoustartaric acid solution is added to the solution, and after stirring forminutes at 60 the cobalt-containing dyestuif formed is precipitated fromthe mass with sodium chloride, filtered ofi, dried and ground. It is adark powder which is soluble in water (more than 50 g./l.) and dyeswool, silk, synthetic polyamide fibers and leather in grayish green-blueshades; being readily soluble in acetone it is also suitable for dyeingspinning solutions of artificial fibers and lacquer media in grey-blueshades.

1 part of the cobalt-containing dyestufi described above is dissolved in4000 parts of water 'at -50. 100 parts of previously wetted wool areentered in this dyebath, 2 parts of 100% acetic acid added dropwise, andthe temperature increased to the boil in 30 minutes and maintained atthe boil for minutes. The dyed wool is then removed, rinsed with waterand dried. A grayish greenblue dyeing is obtained which possessesoutstanding fastness to light, washing, milling, cross dyeing andperspiration.

100 parts of cellulose acetate with a content of 54-55% of splittableacetic acid are mixed with 300 parts of solvent, e.g., a mixture of 275parts of acetone and 25 parts of methanol; and allowed to swellovernight. :Next day 1 part of the cobalt-containing dyestuif of thisexample is dissolved in parts of the same solvent and the solution addedto the cellulose acetate solution with subsequent stirring until 60parts of the solvent have evaporated. After the colored celluloseacetate solution has been filtered. through cotton cloth and cottonpressure filters it is spun into filament in the same way as undyedacetate.

In the following Table I details of the structural composition of someparticularly important homogeneous metal-complex dyestutfs are setforth. In column I the diazo component is named, in column 11 thecoupling component, in column III the metal used for metal-complexformation, and in column IV the shade of the dyeing obtained on wool isnoted.

Table I Diazo component Coupling component Metal (I Shade of dyeing onwool Example No.

2-amino-l-hydroxy-benzene- 4-sulfonlc acid- -carboxy)- phenylamide.

2-am1'no-1-hydroxy-benzene- 5-sulfonie acid- (2-carboxy) phenylamide.

2-(3-chloro)- phenylamlnonaphthalene.

Blue-gray. Or

Neutral gray.

2-(2'-methyl)- phenylaminonaphthalene.

Blue. Gray.

( (II) (I Example Coupling Shade of Diazo component component Metaldyeing on wool 4 z-amlno-l-hy- 2-(2'-methyl)-4- Co Blue-gray.

droxy-benzenechlorophen- Or Neutralgray. -sulfonie acidylaminonaph-(4-oarb0Xy) thalene. phenylamlde.

5 z-amino-l-hy- 2-(4'-methoxy)- Go Blue.

droxy-benzenephenylamino- Cr Gray. fi-sulfom'c aeidnaphthalene.

(3-carboxy)- phenylamide.

6 2-amino-l-hy- 2-benzylamino- Go Blue droxy-tchloronaphthalene.benzeuefi-sultonic acid-(2- carboxy)-phenylamide.

7 2-amino-1-hyz-methylamino- C0 D0.

droxy-benzenenaphthalene. fisulloiiioaeld- 3-car oxy zznaphthylamlde- 8Z-amino-I-hy- Z-amylamlnce 0o Blue-green.

droxy-4-nitronaphthalene benzene-05111- ionlc acid-(2-carboxy)-phenylamide.

9 3-amino-4hy- 2-(3-methoxy)- Co Blue-gray.

droxy-1.1- propylaminodiphenylsulnaphthalene. fone-2-carboxylic acid.

10 3-amino-4-hy- 2-(2-hyd.r0xy)- 00 Do.

droxy-1.1- ethylaminodiphenylketonenaphthalene. 2-carboxylic acid.

11 2-amino-1,4-di- 2-phenylamino- 00 Blue.

methoxybennaphthalene. Or Gray. zene-5-sulfonicacid-(2-oarb0xy)-phenylamide. V

12 Z-amino-l-hy- Z-cyclohexyl- Co Blue-gray.

droxy-benzene-4 aminonaphtha- -sulfome acidlene.

13 Z-amino-l-hy- 3-(4'-ethoxy)- Co Blue-gray.

droxy-benzenephenylamino- Or Gray. 4-sulfonic acidnaphthalene.

, (2-carboxy)- phenylamide.

14 2-amino-1-hy- 2-(3-bromo)- -Co Blue-gray.

droxy benzenephenylamino- 4-sulfonic acidnaphthalene.

N-ethyl-N-(2 carboxy)-phenylamlde.

15 2-amino-l-hy- 2-ethylam1'no- Go Do.

droxy-benzenenaphthalene. 4-sulfonic acid- (2-carboxy-4-chloro)-phenylamide.

16 2-amino-1-hy- 2-lso-propylami- C0 D0.

droxy-benzenenonaphthalene. 4sulf0nic acid- (2carboxy)- phenylamide. 17do 2(2'hydroxy) C0 D0.

7 propylaminonaphthalene.

18 "do 2-(2,4,6-tri- G0 Blue-gray.

methyD-phenyl- Gr Gray. aminonaphthalene.

19 do 2-(3-methoxy)- Cr Gray.

butylamino- Co Blue-gray. napthalene.

20-, do 2-(2 ethoxy)- O0 Bluegray.

ethylaminonaphthalene.

21; do 2-(2.4-dimethyl)- 00 Do,

phenylaminonaphthalene.

99 fin 2-(2.5'-din1ethyl)- Go Do.

phenylaminonaphthalene.

23 do 2- -methyl)- 00 Do.

cyclohexylaminonaphthalene.

24 do 2-phenylethy1a- C0 D0.

mlnonaphthalene.

25 dn 2-(naphthyl-2'- 00 D0.

amino)-naphthalene.

as rln 2-(5'.6'.7 8-tetra- Go Do.

hydronaphthyl- 2-am in naphthalene.

EXAMPLE 27 43.2 parts (0.08 mol) of the metal-free dyestufl? obtainedaccording to Example 1 and 8.4 parts (0.02 mol) of the monoazo compoundobtained by coupling diazomonoazo dyestufi obtained from diazotizedZ-amino-lhydroxybenzene 4 sulfonic acid (2' carboxy) phenylamide and2-phenylamino-naphthalene, 1 part of the monoazo dyestufi produced fromdiazotized Z-aminon acid amide and l-acetoacetized2-am1no-1-hydroxy-4-mtrobenzene with l-dimethyl- 5 1 hydioxybenze e ,4sllfomc tylamrno-Z-ethylhexane, 4 parts of the disazo dyestufiarnmosulfonyl-ammoJ-hydroxynaphthalene are addeo, W

to ether with 14 2 1 arts of or stallized cobaltous sulfate producedfrom dlazouzed S'a O-4hydIOXy-1'1 aloto a melted mass of 60 arts 0% ureaand 60 1 arts of form banana-3 ,'sulfonic acid ids andl-carbo-(r-ethoxyy a P p ethoxyamino-7-hydroxynaphthalene, and 3 partsof crysamide at 100 The whole is stirred for 1 hour, after which time nofurther metal-free d estuff is indicated 10 taluzed cobaltous The mass135 heated for 1 hour The cobalbcoma. d estufi thus fozmed is red Rateat 100, after which time no further metal-free dyestufl" b dflutin the g300 arts of water a then is indicated. It is then diluted with 200 partsof water,

y S p s causing the cobalt-containing dyestufi formed to be prefilteredoff and dissolved with 16 parts of sodium hydroxin 1000 f Water at B theaddition of cipitated. It 18 filtered oil and dissolved with 5 parts of1 0 oreci it ted from; th ysolufion filtered 1 sodium hydroxide in 200parts "of water at 60", then pred g t a d k osder Whic}; is S0111cipitated from this solution with common salt, filtered ofi,

g G1 i than 50 d es W001 Silk dried and ground. It is a dark powderwhich dyes wool, e m er 0 niore silk, synthetic polyamide fibers andleather in blue-green synthetic polyamide fibers and leather 1ngreen-gray Shades shades EXAMPLE 28 In the following Table II details ofthe structural constitution of some particularly important mixed metal-To 50 parts of formamide are added 5 parts of the complex dyestuffs aregiven. In column I the monoazo Table II V) Example M01 Shade of N o.Monoazo compounds of formula I Metallizable azo compounds ratio Metaldyeinglon won 29 2- amino 1 -hydroxy-benzene 4-sulfonic acid-(2-2-aminol-hydroxyfi-nitrobenzenea 2-hydroxy- 1:1 00 Navy blue.

carboxy) phenylamide 2 (3'-chloro) phenylnaphthalene. aminonaphthalene.

30 -do 2 amino 1 hydroxy 5 -nitrobenzene 2hydroxy- 2: 1 1 Go Blue.

naphthalene. 2 amino-l-hydroxy-fi-nitrobenzene 2-phenylaminonaphthalene.

31 do 1-amino-Z-carboxy-benzeneA-stflfonic acid methyl- 2:1 Cr Olive,

anliide 1-(3-chloro)-phenyl-3-methyl-5-pyrazo one.

32 do 3-amino-4hydroxy-1.1-azobenzene-3'-su.lfonic aeid- 1:1 00Blue-o1iv amide 1-carbo-(2'-etl1oxy)-ethoXyamino-7-hy- 1:1 OrOlive-gray. droxynaphthalene.

33 do 2-amino-1-hydroxy-4nitrobenzene l-(dimethyl- 4:1 00 Gray.

amino-sulionyl)-amino-7-hydroxynaphthalene.

34 2amino 1 hydroxy benzene 4 sulfonic acid-(2-2-amino-1-hydr0xy-benzene-4-sulfonic acid amide 6:1 00 Green-blue.

1carboxy)-phenylamide2-phenylaminonaphthal-acetoacetylamino-Z-ethylhexaue.

ene.

35 do 2-az ii lo-l-hydroxy-5-nitrobenzene 2-hydroxynaph 1:1:1 00 Blue.

at ene. 1 amino 2 hydroxy 6 bromonaphthalene 4 sul tonic acid5.8-dichloro-l-hydroxynaphthalene. 36 2 amino 1 hydroxy benzene 4sulronic-acid-(2- 2-amino-1-hydroxy-4-chlorobenzene Z-phenylamil:1:1 CoBlue-gray,

lcal-boxy)phenylaruide 2-phenylaminonaphthanonaphthalene.

ene. 2 amino 1 hydroxy benzene 4 sulionic acid-(2'- carboxy)-phenylamide2(3-chloro)-phenylaminonaphthalene.

37 2-amino l-hydroxy-benzene-4-su1fonic-aeid-(2-2-amino-1'l1ydroxy-4-nitrobenzene-dsulfonic acid 1:2 00 Green-blue.

farboxyyphenylamide 2-phenylaminonaphtha-2-(3-chloro)-phenylaminonaphthalene.

ene.

2 amino l hydrcxy benzene 4 sulfonic acid-(2'- carb0xy)-phenylamide2-(3-cb1oro)-phenylaminonaphthalene. 38"-.."2-amino-1-hydroxy-benzene-4-su1fonic-acid-(2-2-amino-1-hydroxy-5-nitrobenzene 2-aminonaph- 1:1 00 Du,

gar-boxyJ-phenylarnide 2-phenylaminonaphthathalene.

ene. 2 amino 1 -hydroxy benzene 4 sulfonic acid-(2- carboxy)-phenylamide2-(3-chlor0)-phenylaminonaphthalene.

39 z-amino 1 hydroxy 4 sulionic acid-(2-carboxy)-2-amino-1-hydroxy-4-nitrobenzene l-hydroxy-Z- 1:4 (10 Dark-brown.phenylamide 2 phenylaminonaphthalene. acetylamino-i-methylbenzene. 1:2Or Gray-brown,

40 rln 2-amino-1-hydroxy-4-nitrobenzene)2-hydroxynaph- 2:3:1 00Blackthalene. brown.

2 amino -1-hydroxy-benzene-4-sul1onic acid-methylamide) 1 (3-ol1loro)-phenyl-B-methyl-dpyrazolone.

41 do 2 amino 1 hydroxy benzene 4 sulfonic acid- 3:2:1 Cr Khaki.methylamide 1-(3-chloro)-phenyl-3-methyl-5- pyrazolone.

1 amino 2 carboxy benzene 4 sulfonic acidmethylamide1(3-cbloro)-phenyl-3-methyl-5- pyrazolone.

42 2 amino 1 hydroxy benzene 4 sulfonie acid-(2- 3 amino 4-hydroxy1.1-azobeuzene 2-carboxylic 1: 1 :2 60 Brown.

carboxy)-phenylamide 2-(3'-chloro)-pheny1amiacid-a2-hydroxynaphtha1ene.Cr Gray nonaphthalene.

2 amino 1 hydroxy benzene 4 sulfonic acid-(2- 1carboxy)-phenylamitle2-methylaminonaphthaene.

43 2 amino 1 hydroxy 6 nitrobenzene 4 sulionic 3 amino 4 hydroxy1.1-azobenzene 3-sulf0nic 1:1 00 Olive.

acid-(2-carboxy)-phenyl-an1ide 2-phenylaminoacid amidel-dimethylaminosulfonylamino-7- naphthalene. hydroxynaphthalene.

44 2 amino 1 hydroxy 4 chlorobenzene 5 sulfonic do 1:1 00 Do.

acid-(2"carboxy)-phenyl-amide 2-(4-methyl)- phenylamino-naphthalene.

45 2 amino 1 hydroxy benzene 4 sulfonic acid-(2- 3 amino 2 hydroxy 5methyl 1.1-azobenzene- 1:1 00 Blue.

1earboxy)-phenylaruide 2-phenylaminonaphtha- 3-sulIonie acidamide-+2-hydroxynaphthalene. Or Blue-gray.

ene.

45 fin 3-aminoA-hydroxy-1.1-azobenzene 2-hydroxy- 2:1 00 Brown.

naphthalene.

compound of the general Formula I is named, in column H the furthermetallizable azo compounds, in column III the molecular ratio of themonoazo compounds I and the azo'compounds II used, in column IV themetal used, and the shades of the dyeings on wool are noted in column V.5

Formulae of representative dyestuffs of the foregoing examples are asfollows:

EXAMPLE 1 The 1:2 chromium and the 1:2 co balt complex compounds of themonoazo dyestufl? of the =formula OH I I02 v NH and COOH

EXAMPLE 27 EN r in the molecular proportion 4:1:3.

EXAMPLE 34 The 1:2 cobalt mixed complex compounds obtained from themixture of the monoazo dyestufls of the form- The 1:2 cobalt mixedcomplex compounds obtained ulae from the mixture of the monoazodyestufis of the on no i in the molecular proportion of 4: 1.

I EXAMPLE 2s The 1:2 cobalt mixed complex compounds obtained from themixture of the azo dyestuffs of the formulae o a r m 7 OH TQ in themolecular proportion of 6:1.

EXAMPLE 41 The 1:2 chromium mixed complex compounds obtained from themixture of the monoazo dyestuffs of the 60 formulae in the molecularproportion of 3:2:1.

Having thus disclosed the invention what I claim is:

1. A complex metal compound of an azo dyestufi free from sulfonic acidgroups, which contains a metal selected from the group consisting ofchromium and cobalt so bound in complex union to the axo dyestufi thatthe ratio of the number of metal atoms to the molecules of the azodyestufi is about 1:2, the said azo dyestufi corresponding in themetal-free form to the formula yaryleue-C O OH wherein R represents amember selected from the group consisting of hydrogen and lower alkyl;

x represents a member selected from the group consisting of cyclohexyl,methylcyclohexyl, phenylethyl, benzyl, phenyl, chlorophenyl,bromophenyl, lower alkylphenyl, lower di-alkylphenyl, lowertrialkylphenyl and lower alkoxyphenyl;

y represents a member selected from the group consisting ofsulfonylimino and sulfonyl-N-lower alkylimino;

2 represents a member selected from the group consisting of hydrogen,chlorine, nitro and methoxy;

-y-aryleneCOOH stands in one of the positions 4, 5 and 6 of the nucleusA; and

arylene represents a member selected from the group consisting of (a)phenylene, and

(b) chlorophenylene, with the COOH group linked to each of (a) and (b)in one of the positions 2, 3' and 4' relative to y-, and

(c) naphthylene with the COOH group linked in vicinal position to y.

2. A mixed dyestufi consisting essentially of complex metal compounds ofazo dyestuffs free from sulfonic acid groups, which contain molecules oftwo difierent mono azo dyestuffs bound in complex union with atoms of ametal selected from the group consisting of chromium and cobalt, in a2:1 relationship, and in which one of the two monoazo dyestuffscorresponds in the metal-free form to the formula wherein R represents amember selected from the group consisting of hydrogen and lower alkyl;

x represents a member selected from the group consisting of cyclohexyl,methylcyclohexyl, phenylethyl, benzyl, phenyl, chlorophenyl,bromophenyl, lower alkylphenyl, lower di-alkylphenyl, lower tri-alky1-phenyl and lower alkoxyphenyl; z represents a member selected from thegroup consisting of hydrogen, chlorine, nitro and methoxy; -S0NHaryleneCOOH stands in one ofthe positions 4, 5 and 6 of the nucleus A;and arylene represents a member selected from the group consisting of(a) phenylene, and (b) chlorophenylene, with the COOH group linked toeach of (a) and (b) in one of the positions 2', 3' and 4 relative to NH,and (c) naphthylene with the COOH group linked in vicinal position toNH--; and the other monoazo dyestufi corresponds in the metalfree formto the formula wherein R represents the radical of a diazo component ofthe benzene series bearing in ortho-position to the N=N- group asubstituent selected from the group consisting of OH, O- lower alkyl,and

. COOH and R represents the radical of a coupling component selectedfrom the group consisting of a pyrazolone radical substituted with OH inortho-position to the N=N bridge in Formula III,

an acetoacetylamino-alkane radical substituted with OI-I inortho-position to the N=N bridge in Formula III, and

a naphthalene radical substituted in ortho-position to the N=N bridge ofFormula HI with a member selected from the group consisting of OI-I, NHand NHx, wherein x has the same definition as in Formula II.

3. The 1 :2 chromium complex compound of the monoazo dyestuff of theformula EN OH I O 8 i .3 NH

COOH

4. The 1:2 cobalt complex compound of the monoazo dyestuif of theformula s D W8 COOH 5. The 1:2 cobalt mixed complex compounds obtained ex 3 S m m 11 m 1 0% m P 6 mw V m Fm Cd m N N 8 a 0% fig m N I Z l 7 m HI H mm 0 0 M T N m II M a m P 1 m a; Tm m e s I A H 0 0 c c H N o m E P.hf. H H O n T mam N O C M 0 .m m m" m me E o N m M E mm J E p .n D m EH m H N C m C E hfl 0 2t w m m U c e m m k H 07 m P m R i, d H '6 2O d 0mzw m 22 5 m m m m Q Q am 3 f fid 0 M m m d m mm V. my d m O 0O m Tum n0 m mrm O V m NI H Pmmm N m o e H H N n m m e B H w w o m I m m w H .mwmN o o N d m. 1% 0 N ot Q .m film V ,e W 7 m mmmm mm e m om. m m. d fir,a m hm w 50 934,905 Germany Nov. 10, 1955 1,043,546 Germany NOV. 13,1958 SOT-NH; in the molecular proportion of 6: 1.

2. A MIXED DYESTUFF CONSISTING ESSENTIALLY OF COMPLEX METAL COMPOUNDS OFAZO DYESTUFFS FREE FROM SULFONIC ACID GROUPS, WHICH CONTAIN MOLECULES OFTWO DIFFERENT MONOAZO DYESTUFFS BOUND IN COMPLEX UNION WITH ATOMS OF AMETAL SELECTD FROM THE GROUP CONSISTING OF CHROMIUM AND COBALT, IN A 2:1RELATIONSHIP, AND IN WHICH ONE OF THE TWO MONOAZO DYESTUFFS CORRESPONDSIN THE METAL-FREE FORM TO THE FORMULA